Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS4460646 A
Publication typeGrant
Application numberUS 06/359,344
Publication dateJul 17, 1984
Filing dateMar 18, 1982
Priority dateApr 7, 1981
Fee statusPaid
Also published asCA1188025A1
Publication number06359344, 359344, US 4460646 A, US 4460646A, US-A-4460646, US4460646 A, US4460646A
InventorsHiroshi Inoue, Masaaki Isoi, Kazuo Sei
Original AssigneeToa Nenryo Kogyo Kabushiki Kaisha
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Blend of low density ethylene polymer and synthetic rubber reacted with unsaturated carboxylic acid
US 4460646 A
Abstract
The adhesive resin composition and laminate disclosed herein comprises a mixture of linear low density polyethylene, and a synthetic rubber reacted with an unsaturated carboxylic acid or derivative thereof.
Images(6)
Previous page
Next page
Claims(10)
What is claimed is:
1. An adhesive resin composition which comprises a mixture of (A) from 70 to 98 parts by weight of linear low density polyethylene and (B) and from 2 to 30 parts by weight of synthetic olefin or butyl rubber, said mixture being reacted with an unsaturated carboxylic acid or a derivative thereof, said linear low density polyethylene being a copolymer of ethylene and 3 to 14 weight percent alpha-olefin and having a density of 0.915 to 0.935 and the weight-average molecular weight/number-average molecular weight ratio from 3 to 12 and being substantially free of long chain branching.
2. A composition as claimed in claim 1, wherein said alpha-olefin is an olefin selected from the group consisting of butene-1, hexene-1,4-methylpentene-1, and octene-1.
3. A composition as defined in claim 2 wherein the synthetic rubber is a copolymer rubber of ethylene and butene-1.
4. A composition as claimed in claim 1, wherein the synthetic rubber is a copolymer rubber of ethylene and butene-1 or propylene.
5. A composition as claimed in claim 1, wherein the synthetic rubber has a Mooney viscosity of 10 to 150 and a crystallization degree less than 30%.
6. A composition as defined in claim 1, wherein the carboxylic acid is present in a concentration of between 0.01 and 3 weight percent of the composition.
7. A laminate comprising a layer of an adhesive resin composition and a layer of a material selected from the group consisting of a metal and thermoplastic resin, said adhesive resin composition being a mixture of (A) from 70 to 98 parts by weight of linear low density polyethylene and (B) from 2 to 30 parts by weight of synthetic olefin or butyl rubber, said mixture being reacted with an unsaturated carboxylic acid or a derivative thereof, said linear low density polyethylene being a copolymer of ethylene and 3 to 14 weight percent alpha-olefin and having a density of 0.915 to 0.935 and the weight-average molecular weight/number-average molecular weight ratio from 3 to 12 and being substantially free of long chain branching.
8. A laminate comprising:
(a) a layer of a mixture comprising (i) from 70 to 98 weight percent of an adhesive resin composition comprising a linear low density polyethylene which is a copolymer of ethylene and 3 to 14 weight percent alpha-olefin and having a density of 0.915 to 0.935 and being substantially free of long chain branching; and (ii) from 2 to 30 weight percent of a copolymer rubber selected from the group consisting of ethylene/butene-1 and ethylene/propylene, said mixture being reacted with an unsaturated carboxylic acid or derivative thereof; and
(b) a layer of a material selected from the group consisting of a metal and a thermoplastic.
9. A laminate as defined in claim 8, wherein the copolymer rubber is an ethylene-butene-1 copolymer rubber, and the metal is selected from the group consisting of iron, aluminum, copper, zinc, nickel, tin, steel, brass and tinplate.
10. A laminate as defined in claim 8, wherein the thermoplastic is selected from the group consisting of polyamides, polyolefin homopolymers and copolymers, partially acetalized polyvinyl alcohol, partially hydrolyzed ethylene-vinyl acetate copolymer, polyesters and polyvinyl chloride.
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an adhesive resin composition and a laminate composed thereof. More particularly, the present invention relates to adhesive polyethylene-synthetic rubber composition.

2. Description of the Prior Art

Heretofore, it has been proposed to coat synthetic resins on metal pipes, metal plates, electric wires and cables, and wires in order to improve the corrosion resistance, external appearance, and food sanitation of metals, or to make laminates in combination with other resins in order to remedy the drawbacks inherent in a variety of synthetic resins. Physically and chemically superior polyolefins are considered to be promising for lamination with metals or synthetic resins. However, the non-polar polyolefins do not bond easily to metals and resins. In order to eliminate such a drawback, various means have been proposed.

For instance, Japanese unpatented Publication No. 52-8035 (1977) discloses a method for adding 1 to 20 wt. % of a rubber compound to high-pressure low-density polyethylene, low-pressure high-density polyethylene, or polypropylene and then modifying the mixture with an unsaturated carboxylic acid. Japanese unpatented Publication Nos. 54-82 (1979) and 54-83 (1979) disclose a method for laminating a modified polyolefin to nylon, polyester, or ethylene-vinyl acetate copolymer. According to this method modification is accomplished by reacting an unsaturated carboxylic acid or a derivative thereof with a mixture of 70 to 98 wt. % of high-pressure low-density polyethylene, low-pressure high-density polyethylene, or polypropylene and 30 to 2 wt. % of an ethylene-alpha-olefin copolymer having a crystallization degree less than 30%. According to these prior art technologies, an improvement is made in adhesiveness but the improvement in environmental stress cracking resistance (ESCR) and high-speed tensile elongation is not necessarily satisfactory.

SUMMARY OF THE INVENTION

In order to overcome the above-mentioned disadvantages, the present inventors carried out a series of researches which led to the findings that an adhesive polyolefin which is superior in ESCR, tensile strength, elongation, flowability, and toughness is obtained by reacting an unsaturated carboxylic acid or a derivative thereof with a mixture of linear low density polyethylene copolymer (abbreviated as L-LDPE hereunder) and synthetic rubber. The present invention is based on these findings.

The invention contemplates an improved adhesive resin composition and an improved laminate defined as follows:

(1) an adhesive resin composition which comprises a mixture of (A) linear low density polyethylene and (B) synthetic rubber, said mixture being reacted with an unsaturated carboxylic acid or a derivative thereof, said linear low density polyethylene being a copolymer of ethylene and alpha-olefin and having a density of 0.915 to 0.935 and the weight-average molecular weight/number-average molecular weight ratio (abbreviated as Mw/Mn hereunder) from 3 to 12, and

(2) a laminate comprising an adhesive resin composition and a metal or thermoplastic resin, said adhesive resin composition being a mixture of (A) linear low density polyethylene and (B) synthetic rubber, said mixture being reacted with an unsaturated carboxylic acid or a derivative thereof, said linear low density polyethylene being a copolymer of ethylene and alpha-olefin and having a density of 0.915 to 0.935 and the Mw/Mn ratio from 3 to 12.

The adhesive resin composition of the present invention exhibits superior properties in ESCR, tensile strength, elongation, impact strength, bond strength, and flowability. It, accordingly is ideally suited for use in laminates.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The L-LDPE used in this invention is produced by copolymerizing ethylene with alpha-olefin selected from the group consisting of butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, and octene-1, and preferably from the group consisting of butene-1, hexene-1, 4-methylpentene-1, and octene-1, at a ratio of 3 to 14 wt. % in the presence of a chromium catalyst or Ziegler catalyst by the gas phase method, liquid phase method, or solution method. L-LDPE thus produced has a density of 0.915 to 0.935, an Mw/Mn ratio of 3 to 12, and an MI of 0.1 to 50 g/10 min. [as measured by ASTM D-1238E (190° C., 2160 g); the same shall apply hereunder]. Most preferable among them is one which is produced by the gas phase method.

The synthetic rubber used in this invention includes a copolymer rubber of ethylene and an alpha-olefin selected from the group consisting of propylene, butene-1, pentene-1, hexene-1, octene-1, and 4-methylpentene-1; ethylene-propylene-nonconjugated diene rubber (EPDM), isoprene rubber (IR), butyl rubber (BR), and styrene-butadiene thermoplastic rubber (SBR). Preferable among them is ethylene-alpha-olefin copolymer rubber, and most preferable is ethylene-butene-1 copolymer rubber (EBR). These synthetic rubbers should preferably have a Mooney viscosity of 10 to 150 (ML1+4 100° C., JIS K6300 [the same shall apply hereunder]), and a crystallization degree less than 30%. Such ethylene-alpha-olefin copolymer rubbers have usually a density lower than 0.9.

The synthetic rubber should preferably be incorporated in an amount of 30 to 2 parts by weight to 70 to 98 parts by weight of L-LDPE. Synthetic rubber less than 2 parts by weight is not enough to improve ESCR, and synthetic rubber more than 30 parts by weight improves ESCR at the sacrifice of mechanical strength of the resulting product.

The unsaturated carboxylic acid used in this invention includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, endo-bicyclo[2,2,1]-1,4,5,6,7,7-hexachloro-5-heptene-2,3-dicarboxylic acid, endo-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid. The derivative of carboxylic acid used in this invention includes aced anhydrides and esters, such as maleic anhydride, citraconic anhydride, endo-bicyclo[2,2,1]-1,4,5,6,7,7-hexachloro-5-heptene-2,3-dicarboxylic acid anhydride, endo-bicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and maleate esters (monoester and diester).

The aforesaid unsaturated carboxylic acid or derivative thereof should preferably be added to L-LDPE in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of said mixture of L-LDPE and synthetic rubber. These quantities result in the content of 0.05 to 3 wt. % of unsaturated carboxylic acid or derivative thereof in the resulting adhesive resin composition. If the content of the unsaturated carboxylic acid or a derivative thereof in the resulting composition is less than 0.01 wt. %, no improvement is made in adhesion; and conversely, if it is more than 3 wt. %, no further improvement is made in adhesion but gels and discoloration occur.

The reaction of aforesaid mixture of L-LDPE and synthetic rubber with an unsaturated carboxylic acid or a derivative thereof can be accomplished by any known method. For instance, aforesaid mixture of L-LDPE and synthetic rubber is mixed with an unsaturated carboxylic acid or a derivative thereof and an initiator of organic peroxide by a Henschel mixer or ribbon blender and then melted and kneaded by a Banbury mixer or a single- or multi-screw extruder at a temperature higher than the melting point of polyethylene but lower than 250° C. Examples of organic peroxides include di-t-butyl peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)-hexyne-3, dicumyl peroxide, and benzoyl peroxide. For synthetic rubber in the form of bale, a Banbury mixer or roll mill is suitable for heating, melting, and mixing. The reaction may be carried out in such a manner that aforesaid mixture of L-LDPE and synthetic rubber is dissolved in a solvent and an unsaturated carboxylic acid or a derivative thereof and an initiator are added to the solution. The initiator should preferably be added in an amount of 0.001 to 0.5 part based on 100 parts of the mixture of L-LDPE and synthetic rubber.

The synthetic rubber in the composition of this invention may be modified previously by aforesaid unsaturated carboxylic acid or a derivative thereof.

The adhesive resin composition thus obtained may be used alone or in combination with L-LDPE, synthetic rubber, or modified products obtained by reaction with an unsaturated carboxylic acid or a derivative thereof. For example, the composition of this invention may be blended with (1) L-LDPE and/or synthetic rubber, (2) modified L-LDPE and/or modified synthetic rubber reacted with an unsaturated carboxylic acid or a derivative thereof, or (3) a mixture of L-LDPE and/or synthetic rubber and modified L-LDPE and/or modified synthetic rubber. These compounds may be mixed with the composition of this invention, followed by melting and kneading. The ratio of L-LDPE, synthetic rubber, and unsaturated carboxylic acid or derivative thereof added in the final composition should be 70 to 98 parts by weight, 30 to 2 parts by weight, and 0.01 to 3 wt. %, respectively, for reasons mentioned above.

Metals used for making the laminate of this invention include iron, aluminum, copper, zinc, nickel, tin, stainless steel, brass, galvanized steel, and tinplate. Thermoplastic resins used for making the laminate of this invention include polyamides such as nylon-6, nylon-66, nylon-11, nylon-12, nylon 6-10; polyolefin homopolymers or copolymers such as polypropylene and polybutene; partially acetalized polyvinyl alcohol (vinylon); partially hydrolyzed ethylene-vinyl acetate copolymer (eval); polyesters such as polyethylene terephthalate and polybutylene terephthalate; and polyvinyl chloride. Preferable among them are nylon and vinylon.

The laminate of this invention is obtained by laminating the composition of this invention or a mixture in which the composition of this invention is incorporated with unmodified or modified L-LDPE and/or synthetic rubber, with a member selected from the above-mentioned metals or thermoplastic resins.

The laminate of this invention can be produced by any known method; for example, a method for heat bonding members which have been previously formed into a film or sheet, a method for laminating layers outside the die, a method for laminating layers inside the die (coextrusion), an extrusion coating method, and powder coating. Usually, the metal layers to be laminated undergo preliminary treatment such as degreasing with solvent, pickling, shot blasting, and bonderizing. High bond strength between layers can be achieved by applying an epoxy resin primer. A modified epoxy resin primer of one-part system or two-part system is preferable from the standpoint of heat resistance and stability.

The laminate of this invention is basically of two-layer structure including one layer of the composition of this invention or a mixture containing as a major ingredient the composition of this invention and the other layer selected from the aforesaid metals and thermoplastic resins. Various combinations are possible as required. For example, the composition/a metal; the composition/a thermoplastic resin; a metal/the composition/a metal; a metal/the composition/a thermoplastic resin; and a thermoplastic resin/the composition/a thermoplastic resin. In addition, it is also possible to combine layers of other substances such as fiber, paper, and wood.

The adhesive resin composition of this invention adheres to aforesaid metals or thermoplastic resins with a high bond strength. Moreover, because of high flowability it can be used for powder coating, extrusion coating, and extrusion molding. Being superior in bond strength, ESCR, high-speed tensile elongation and toughness, the adhesive resin composition can also be used for coating of steel wires, electric wires, cables, metal plates, metal pipes, and metal inserts, and for lamination with multilayer films and sheets formed by coextrusion with a variety of resins and multilayered bottles and containers formed by multilayer blow molding.

The composition of this invention may be incorporated, as required, with a weathering agent, heat stabilizer, molding aid, anti-oxidant, colorant, and the like.

The invention is described in detail by the following examples. In Examples and Referential Examples, "parts" means "parts by weight", and the peel strength (which indicates adhesiveness), high-speed tensile elongation, and melt tensile strength were measured by the following methods.

(1) Peel strength

Preparation of test piece

(A) Aluminum laminate

A three-layered laminate consisting of two aluminum sheets (0.1 mm thick) sandwiching an intermediate layer (0.1 mm thick) of the composition, was cut into a 25 mm wide specimen.

(B) Steel laminate

A two-layered laminate consisting of a bonderized steel plate (3.2×50×150 mm) and a layer (1 mm thick) of the composition, was cut into a 10 mm wide specimen. A gripping surface was formed by removing the resin layer, up to 20 mm from the end, using a sharp knife.

(C) Nylon laminate

A three-layered laminate consisting of two nylon-6 layers (0.1 mm thick) sandwiching an intermediate layer (0.1 mm thick) of the composition, was cut into a 25 mm wide specimen.

These specimens were measured for 90° peel strength on an Instron type universal tester.

(2) ESCR (in comformity with ASTM D-1693)

(A) Test piece: 38×12.7×2 mm

(B) Surface active agent: 10% aqueous solution of Igepal

(C) Test temperature: 50° C.

(3) High-speed tensile elongation (JIS K6760)

(A) Rate of pulling: 500 mm/min. ±10%

(4) Melt tensile strength

The flowability was evaluated by measuring the tensile force required to pull at a constant rate the molten resin extruded from the orifice of a melt indexer under the following conditions.

(A) Orifice: 2.095 mmφ×8 mm

(B) Test temperature: 190° C.

(C) Extrusion rate of resin: 10 mm/min.

(D) Take-up rate of resin: 5.5 m/min.

(5) Resistance to salt water

The adhesion to a metal substrate was evaluated with a laminate test specimen prepared as follows: A pretreated iron plate, measuring 3.2 mm thick, 50 mm wide, and 150 mm long, was coated with an epoxy primer to a thickness of about 10 microns, followed by heating in an oven at 250° C. The hot iron plate was coated by fluidized-bed coating with powder of the resin composition, followed by curing in an oven. The coating thickness was 0.8 to 1.0 mm. After cooling, a rectangular cut, measuring 30 mm×100 mm, was made on the resin layer. This test specimen was dipped in a constant temperature bath at 50° C. containing 3% salt solution, and the time for the resin layer to come off from the substrate was measured.

EXAMPLES 1 to 12

The compositions of this invention were prepared by mixing at the ratios as shown in Table 1 L-LDPE, ethylene-butene-1 copolymer rubber (referred to as EBR hereunder, density: 0.880, MI: 4.0) or ethylene-propylene copolymer rubber (referred to as EPR hereunder, density: 0.880, MI: 4.0), maleic anhydride, acrylic acid, or endo-bicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid anhydride (referred to as himic acid hereunder), and 2,5-dimethyl-2,5-di-(t-butylperoxy)-hexyne-3 (initiator). The resulting mixture was then melted and kneaded by an extruder at 220° C.

Table 1 shows the physical properties of the composition and peel strength of the laminates composed of the compositions and aluminum, iron, or nylon.

REFERENTIAL EXAMPLES 1 to 6

For comparison, modified L-LDPE alone, modified low-density polyethylene (LDPE) alone, modified high-density polyethylene (HDPE) alone, and a modified mixture of LDPE and EBR used in Example 1 were measured for physical properties and peel strength as in Example 1. The results are shown in Table 2.

                                  TABLE 1__________________________________________________________________________1   2   3    4    5    6    7    8    9    10   11   12__________________________________________________________________________95  95  75   90   90   90   85   90   90   90   90   9012.0    12.0   12.0 12.0 12.0 12.0 12.0 5.0  2.0  8.0  4.0  12.00.926    0.926   0.926        0.926             0.926                  0.926                       0.926                            0.934                                 0.920                                      0.926                                           0.926                                                0.9265.0 5.0 5.0  5.0  5.0  5.0  5.0  6.0  6.0  5.0  5.0  5.0Bu  Bu  Bu   Bu   Bu   Bu   Bu   Bu   Bu   Pe   Oc   BuEBR 5    EBR 5   EBR 25        EBR 10             EBR 10                  EBR 10                       EBR 15                            EBR 10                                 EBR 10                                      EBR 10                                           EBR 10                                                EBR 10MA  MA  MA   MA   HM   AA   MA   MA   MA   MA   MA   MA0.3 0.1 0.3  0.3  0.6  0.5  0.3  0.3  0.3  0.3  0.3  0.30.025    0.025   0.025        0.025             0.025                  0.025                       0.025                            0.025                                 0.025                                      0.025                                           0.025                                                0.0257.0 7.0 5.8  7.0  6.9  6.8  6.3  3.6  1.7  3.5  3.0  7.00.924    0.924   0.913        0.922             0.922                  0.922                       0.919                            0.929                                 0.916                                      0.921                                           0.921                                                0.9210.28    0.09   0.28 0.28 0.50 0.47 0.27 0.27 0.26 0.27 0.27 0.28500 500 >1000        >1000             >1000                  >1000                       >1000                            >1000                                 >1000                                      >1000                                           >1000                                                300700 700 700  700  700  700  700  700  700  700  700  5500.7 0.7 0.8  0.7  0.7  0.7  0.8  1.0  2.0  1.0  1.3  0.76.0 6.0 7.0  6.5  6.5  6.0  6.0  6.0  7.0  7.0  7.0  6.04.5 4.5 5.5  4.5  5.0  5.0  5.5  5.5  6.0  6.0  6.5  5.012.0    10.0   17.0 14.0 14.0 13.0 15.0 15.0 16.0 15.0 16.0 13.0__________________________________________________________________________ Butene-1, Oc: Octene1, Pe: Pentene1 Maleic anhydride, HM: Himic acid, AA: Acrylic acid

                                  TABLE 2__________________________________________________________________________Example No.      1    2    3    4   5   6__________________________________________________________________________(type)     L-LDPE           L-LDPE                L-LDPE                     HDPE                         LDPE                             LDPE(parts)    100  100  100  100 100 90MI (g/10 min)      12.0 5.0  12.0 8.0 10.0                             10.0Density (g/cc)      0.926           0.934                0.926                     0.960                         0.919                             0.919--Mw/--Mn  5.0  6.0  7.0  --  --  --Comonomer* Bu   Bu   Pe   --  --  --EBR (parts)      0    0    0    0   0   10Unsaturated      MA   MA   MA   MA  MA  MAcarboxylic acid**Quantity (parts)      0.3  0.3  0.3  0.3 0.3 0.3Perhexyne-2,5-      0.025           0.025                0.025                     0.025                         0.025                             0.025benzoyl (parts)Physical Propertiesof adhesive compoundMI (g/10 min)      7.6  4.0  7.0  3.0 6.5 5.0Density (g/cc)      0.926           0.934                0.926                     0.960                         0.919                             0.915Q'ty of carboxylic      0.28 0.28 0.28 0.21                         0.26                             0.26acid added (wt %)ESCR F50 (hours)      7.0  25.0 30.0 1(-)                         1(-)                             4.0High-speed tensile      400  480  550  20  280 500elongation (%)Melt tensile      0.7  1.0  0.8  2.0 4.0 4.5strength (g)Peel strengthFe (kg/cm) 5.1  6.0  5.5  2.5 2.0 4.0Al (kg/2.5 cm)      4.5  5.0  4.8  3.0 2.5 3.0Nylon-6 (kg/2.5 cm)      11.0 11.0 11.0 4.0 4.0 6.0__________________________________________________________________________ Note: *Bu: Butene1, Pe: Pentene1 **MA: Maleic anhydride
EXAMPLES 13 and 14

The adhesive resin composition obtained in Example 4 was incorporated at the ratios shown in Table 3 with L-LDPE and ethylene-butene-1 copolymer rubber as used in Example 1. The resulting compositions were measured for physical properties and 90° peel strength. The results are shown in Table 3.

              TABLE 3______________________________________Example No.        13      14______________________________________Adhesive resin com-              40      20position (parts)L-LDPE (parts)     54      72Ethylene-butene-1 co-              6       8polymer rubber (parts)Physical Propertiesof adhesive compoundMI 190° C. (g/10 min)              7.6     8.0Density (g/cc)     0.922   0.922Q'ty of carboxylic 0.11    0.05acid added (wt %)ESCR F50 (hours)              >1000   >1000High-speed tensile 700     700elongation (%)Melt tensile       0.6     0.5strength (g)Peel strengthFe (kg/cm)         6.0     6.0Al (kg/2.5 cm)     5.5     5.0Nylon-6 (kg/2.5 cm)              12.5    11.0______________________________________
EXAMPLES 15 to 23

The composition obtained in Example 1 was evaluated for resistance to salt water by varying the pretreatment and primer. The laminate specimens with a coating thickness of 0.8 mm were prepared by fluidized-bed coating at 250° C. The specimens were dipped in 3% sodium chloride solution at 50° C. The results are shown in Table 4.

              TABLE 4______________________________________                           Initial                                  Resist-Ex-                      Cooling                           bond   ance toam-                      after  strength                                  salt waterple  Pretreatment            Primer  coating                           (kg/cm)                                  (hour)______________________________________15   Calcium phos-            Epoxy   Water  12.0   360phate BP-602        cooling16   Calcium phos-            Epoxy   Natural                           12.5   >720phate BP-402        cooling17   Calcium phos-            Epoxy   Natural                           12.5   >720phate BP-602        cooling18   Shot blast- Epoxy   Natural                           7.5    >720ing #60             cooling19   Pickling    Epoxy   Natural                           5.0    48015% HCl             cooling20   Degreased   Epoxy   Water  3.0    240by trichlene        cooling21   Shot blast- None    Natural                           3.0     48ing #60             cooling22   Calcium phos-            None    Natural                           6.0     72phate BP-602        cooling23   Zinc phos-  None    Water  5.5     48phate BP-402        cooling______________________________________
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3987122 *Sep 27, 1974Oct 19, 1976Exxon Research And Engineering CompanyThermoplastic adhesive compositions
US4088714 *Aug 16, 1976May 9, 1978Exxon Research & Engineering Co.Cross-linked melt-flowable thermoplastic elastomer blend comprising EPR or EPDM, polyethylene and polypropylene
US4255533 *Sep 28, 1978Mar 10, 1981Exxon Research & Engineering Co.Polyethylene-butyl rubber blend grafted with acrylic acid
US4283317 *Sep 15, 1980Aug 11, 1981E. I. Du Pont De Nemours And CompanyWax-free, hot melt adhesive compositions
JPS505482B1 * Title not available
JPS5025845B1 * Title not available
JPS5164257A * Title not available
JPS5240083A * Title not available
JPS5488447A * Title not available
JPS50121058A * Title not available
JPS50136735A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4629648 *Oct 1, 1985Dec 16, 1986Minnesota Mining And Manufacturing Co.Chalk body in melt fusion with polymer
US5055526 *Oct 28, 1988Oct 8, 1991Mitsui Petrochemical Industries, Ltd.Adhesive resin compositions and laminates utilizing same
US5247018 *May 20, 1992Sep 21, 1993Mitsui Petrochemical Industries, Ltd.Thermoplastic resin of elastomer composition having excellent paint adhesion and laminate comprising layer of said thermoplastic elastomer and polyurethane layer
US5744250 *Dec 6, 1996Apr 28, 1998E. I. Du Pont De Nemours And CompanyFirst layer is an inomer or acid copolymer, second layer is of thermoplastic base polymer containing ethylene-alpha olefin polymer and elastomer grafted with unsaturated caraboxylic acid and derivatives; used for packaging
US6258308May 14, 1999Jul 10, 2001Exxon Chemical Patents Inc.Process for adjusting WVTR and other properties of a polyolefin film
US6264864Oct 14, 1999Jul 24, 2001Exxon Chemical Patents Inc.Process for producing polyolefin microporous breathable film
US6706228Jun 18, 2001Mar 16, 2004Exxonmobil Chemical CompanyProcess for producing polyolefin microporous breathable film
US6843949Feb 11, 2003Jan 18, 2005Tredegar Film Products CorporationProcess for adjusting WVTR and other properties of a polyolefin film
US6953510Oct 14, 1999Oct 11, 2005Tredegar Film Products CorporationMethod of making microporous breathable film
US7462391 *May 17, 2006Dec 9, 2008The Goodyear Tire & Rubber CompanyMulti-layered veneer for a tire sidewall
EP0217637A2 *Sep 25, 1986Apr 8, 1987Minnesota Mining And Manufacturing CompanyExtruded caulk strip
EP0315418A2 *Nov 1, 1988May 10, 1989Mitsui Petrochemical Industries, Ltd.Adhesive resin compositions and laminates utilizing same
EP0365266A2 *Oct 17, 1989Apr 25, 1990Nippon Petrochemicals Company, LimitedMulti-layered blow-molded bottle
EP0713765A2 *Nov 13, 1995May 29, 1996Wolff Walsrode AgSterilisable, deep-drawable, adhesive-free and sealable composite film comprising polyolefins or their copolymers
WO1996030455A1 *Mar 26, 1996Oct 3, 1996Du PontCo-extrudable adhesives with good age-down resistance
Classifications
U.S. Classification428/344, 525/193, 156/334, 428/343, 428/355.0AC, 428/355.00R, 428/355.0EN
International ClassificationC09D5/03, B32B15/08, C08L101/00, C08L21/00, C09J123/08, B32B15/085, C08L23/00, C09J123/16, C08F8/46, C08L7/00, B32B27/04, B32B27/32, C08L23/26, C09J123/26
Cooperative ClassificationC09J123/0815, B32B27/04
European ClassificationC09J123/08A1, B32B27/04
Legal Events
DateCodeEventDescription
Dec 18, 1995FPAYFee payment
Year of fee payment: 12
Dec 20, 1991FPAYFee payment
Year of fee payment: 8
Jan 29, 1988FPAYFee payment
Year of fee payment: 4
Apr 30, 1984ASAssignment
Owner name: TOA NENRYO KOGYO K.K., TOKYO, JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:INOUE, HIROSHI;ISOI, MASAAKI;SEI, KAZUO;REEL/FRAME:004251/0926
Effective date: 19820226